Hair spray containing vinyl ester-ester of {60 ,{62 -unsaturated mono-or dicarboxylic acid copolymer

ABSTRACT

Hair sprays containing film forming copolymers of (a) vinyl esters; (b) monoesters of aliphatic olefinically unsaturated mono- or dicarboxylic acids with lower alkanediols, and where required; and (c) Alpha , Beta -unsaturated carboxylic acids are disclosed.

Umted States Patent 1 1 1 3,723,616 Erlemann et al. Mar. 27, 1973 Y [54]HAIR SPRAY CONTAINING VINYL [51] Int. Cl. ..A6lk 7/10 ESTER ESTER OFaBJINSATURATED [58] Field of Search ..424/DIG. 1, DIG. 2, 47, 71;MONO-0R DICARBOXYLIC ACID 260/785 3 COPOLYMER [56] References Cited [75]Inventors: Gustav Erlemann, Basel, Switzerland; Manfred Sander; GerhardUNITED STATES PATENTS Zimm", both of Kelkheim, 3,208,963 9/1965 Jasinski260/8075 x y 3,247,145 4/1966 Masters et al. .....260/23 3,272,7859/1966 Lewis et a1. ....260/80.75 [73] Assgnee' g Roche Nutley 3,577,5175/1971 Kubot et al ..424 47 [22] Filed: Feb. 27, 1970 PrimaryExaminer-Albert T. Meyers Assistant Examiner-Vera C. Clarke [21] Appl'15258 Attomey-Sa.muel L. Welt, Jon S. Saxe, Bernard S. Related USApplication Data Leon, Gerald S. Rosen and R. l-lain Swope [62] Divisionof Ser. No. 652,408, July ll, 1967, aban- [57] ABSTRACT one Hair sprayscontaining film forming copolymers of (a) [30] Foreign ApplicationPriority Data vinyl esters; (b) monoesters of aliphatic olefinicallyunsaturated monoor dicarboxylic acids with lower al- July 29, 1966Switzerland ..1 1014/66 kanediols and where required; and (c) a B-unaturated carboxylic acids are disclosed. [52] US. Cl. ..424/47, 260/33.4R, 260/33.6 UA,

260/338 UA, 260/785 BB, 260/8075, 260/808, 260/8081, 260/861 E, 424/DIG.l, 424/DIG. 2, 424/71 1 Claim, No Drawings HAIR SPRAY CONTAINING VINYLESTER-ESTER OF a,B-UNSATURATED MONO-OR DICARBOXYLIC ACID COPOLYMERRELATED CASES This case is a division of our US. Pat. application, Ser.No. 652,408, filed July I1, 1967, and now abandoned.

BACKGROUND OF THE INVENTION Film forming substances used as hairfixatives or setting agents should be soluble both in water and inalcohols since preparations for hair setting are used as solutions inwater-alcohol mixtures. Water solubility of the film former is desiredeven when a purely alcoholic preparation such as, for example, asprayable preparation is used, in order that it can be readily removedfrom the hair, e.g., by shampooing.

Substances which are to be used as film formers for sprayable hairfixatives must fulfill a number of requirements, i.e., they must be goodfilm formers and adhere well to the hair; they must have good solubilityin the lower molecular weight solvents which are usually used in suchpreparations, e.g., ethanol and isopropanol; they must be miscible andcompatible with the various propellants used in hair sprays, e.g.,polyhalogenated lower hydrocarbons; they must give a glossy and clearfilm which is sufficiently flexible to hold the hair in placepermanently despite the usual movements of the head or in wind, on theother hand, the film must be sufficiently brittle so the hair can bereadily combed and brushed without collapsing and loss of the hair setthrough complete removal of the film coating; they must give a filmwhich is soluble in cold water but which does not become sticky in moistatmospheres and, finally, they must be physiologically inoffensive. Apolymer which is to be used as a hair fixative in the form of an aerosolpreparation must thus, on the one hand, be water soluble or at leastcapable of swelling therein and therefore be removable by the usualshampoos, while, on the other hand, it must, at least in combinationwith organic solvents, be soluble in the liquid propellant medium. Thesolution of the polymer when sprayed on the hair should dry out to aglossy and clear film which is flexible and the film should adhere wellto the hair in order to achieve a long-lasting action of the hairfixative.

The polymers hitherto used as film formers in hair dressing agents havenumerous disadvantages. Many have the desired solubility properties but,as a consequence of high hygroscopicity, give the hair a sticky feel athigh humidities. Other polymers have good hygroscopicity, but exhibitunsatisfactory solvent properties particularly being difficulty solublein the alcohol-propellant mixtures generally used for hair sprays. Somepolymers, however, have good hygroscopicity and are sufficiently solublein the alcoholpropellant mixtures, but are not sufficientlywater-soluble and therefore are difficult to wash out of the hair. Otherpolymers do not adhere to the hair well with the result that the hair towhich it is applied sticks together and the individual hairs are notset-so that when the hair is combed, it loses its set and collapses.

SUMMARY OF THE INVENTION It has been discovered, according to thisinvention, that the properties required of film forming copolymers,particularly those intended for use in hair preparations, are fulfilledby film forming copolymers based on vinyl esters, hereinafter defined.This invention also comprehends hair fixatives containing the copolymersof this invention having carboxyl groups wholly or partially neutralizedby salt-formation. In another aspect, this invention comprehendssprayable hair fixtures which contain the copolymers dissolved in amixture of water-miscible solvents, advantageously lower alcohols andpolyhalogenated lower hydrocarbons.

DETAILED DESCRIPTION OETI-IE INVENTION The film forming copolymers ofthisinvention are based on vinyl esters and contain essentiallythefollowing components:

a. from about 90 to 40 percent by weight,preferably about to 60 percentby weight of a vinyl ester or mixture of vinyl esters of the generalformula ing up to seven carbon atoms with lower alkanediols containingup to four carbon atoms and c. from about 0 to 10 percent by wetsaturated carboxylic acid of the general formula this invention containas component (a) essentially vinyl esters with up to seven carbon atoms,it is to be understood that part of said component (a) can have a highermolecular structure. It has been found that said component (a) maycontain up to 25 percent of vinyl esters derived from acids with up to18 carbon atoms.

Examples of suitable esters defined by component (b) are those ofa,B-unsaturated monoand dicarboxylic acids, e.g., acrylic acidmonoethyleneglycol ester, methacrylic acid monoethyleneglycol ester,crotonic acid monoethyleneglycol ester, crotonic acidmonopropyleneglycol ester, maleic acid ght of an a,B-unacid ble for useas component (c) are acrylic ,acid,

methacrylic acid, a-chloroacrylic acid, maleic acid, fumaric acid,crotonic acid and the like. Particularl suitable is'crotonic acid(B-methacrylic acid).

' When monohydroxyalkyl esters of dicarboxylic acids are used ascomponent'(b), it is not necessary to use component (c) unless specificproperties are required since there are sufficient free carboxyl groupspresent.

Especially preferred are copolymers of vinyl acetate and/or vinylpropionate, fl-methacrylic acid B-hydroxyethyl ester and B-methacrylicacid.

The amounts by weight of the components of the copolymerizates aregoverned by the desired properties of the end products.

Thus, component (a) affects the solubility of the end product so thatthe more of component(a) present the better the solubility in organicsolvents and, the less the solubility in water and vice versa. The watersolubility, however, is increased primarily by the content of component(c) and only secondarily by the content of component (b). The ethanolsolubility depends for the most part on the content of component (b).The type of vinyl said copolymers. Additional regulators. such asbutyraldehyde or mercaptans. can be used to obtain copolymers with stilllower molecular weight, which are of special value for certain purposes.One criterion generally used to characterize the molecular weight ofpolymers is the limiting viscosity number (or intrinsic viscosity),which is obtained by extrapolating to zero concentration the Hugginsequation for the viscosity the products obtained will be. .In order toachieve the desired consistency, it is preferred .to use'mixtures ofvinyl esters. u

A convenient composition is the following:

About 90 to 40 parts by weight (preferably 80 to 60 parts by weight) ofcomponent'(a), e.g., a vinyl esteror of a vinyl ester mixture whosecomposition is determined by the desired consistency of the end product,about 10 to 60 parts by weight (preferably 20 to 40 parts by weight) ofcomponent (b), e.g., a monoester of a substituted or unsubstitutedaliphatic, olefinically unsaturated mon'oor .dicarboxylicacid and aboutOto l0 parts'by weightof component (c), e.g.,an nip-unsaturatedcarboxylicacid, are used per 100 parts by weight of component mixture. i

lnthe event-it is .desiredto make'the end products substantially watersoluble,,itis necessary to neutralize the carboxyl groups presentinthe'copolymer. This can be accomplished with a base, e.g.,.diethanolamine,

triethan'olamine, .2-amino-2-methyl- 1,3-pro'panedioi of thisinvention.Such solvents can also be used as regulators,-since they limit,depending uponkind and amount, the molecular weight .of the resultingcopolymers, thus providing for a complete solubility of number (orspecific viscosity). Organic and inorganic peroxides, alone or withaccelerators, can be used as free radical initiatorsgtypical suitablefree radial initiators are, e.g., peroxides, such as, dibenzoylperoxide,

dilauroyl peroxide, potassium peroxydisulphate orthermolabile freeradical forming compounds, e.g., azodiiso-butyronitrile. I

The copolymerization reaction is carried out in the absence of oxygen instirring vessels fitted with reflux condensers. In this process allcomponents of the monomer mixture can either be added to the oxygen- Ifree solvent simultaneously with the initiators, or alternativelyindividual components of the monomer'mixture, mixed with'a portion ofthe initiators can be added during the reaction. The polymerization isgenerally initiated by heating the contents of the flask at reflux'cordance with the invention as component (b) can be made by conventionalmeans, e.g., byrreaction of the appropriate carboxylic acids withethylene oxide or simple alkyl derivatives thereof.

The copolymers produced by theiprocess-of thisin- I vention are suitablefor use. infhair sprays used to retain hair set without encountering,theproblems of -solubility, consistency and elasticity mentionedpreviously. These copolymers can also be prepared for usein combinationwith water miscible solvents and can'be 1 soluble in liquefied polyhalogenated hydrocarbons which are gaseousat normal'temperature andpressure. P

lt hasbeen found that the hair fixative in accordance with the inventionnot only fulfills the conditions necessary for an aerosol preparation,especially, good adhesion to the hair, but also inhibits the formationof scale. on the comb and hair.

The properties of the end products other than solubility which arecontrolled by suitable choice of the starting. components (a), (b)and"(c)are consistency and elasticity. I I Thecomposition of'the vinylester component (a) determines the elasticity" and consistency, i.e.,softness" or hardness of the endfproducts. As stated above thecopolymerisate'becomes the softer the more the carbon content of theacid component in the vinyl ester is increased and the copolymerisatebecomes the harder the more branched said acids are. It ,is convenient,instead of a single vinyl ester, tochooseas the copolymerizationcomponent a mixture of vinyl esters so that the desired consistency isobtained, e.g., vinyl acetate and vinyl propionate or mixtures of one ofthem with vinyl esters of higher aliphatic carboxylic acids with up tofive carbon atoms. It has proved advantageous if about 5 to 25 percentof said vinyl ester was derived from higher molecular acids with up to18 carbon atoms, such as acids with 9, l1 and 18 carbon atoms. The typeof compound employed as components (b) and (c) in the reaction mixturelikewise determines the consistency of the end product, depending ontheir proportion, and to a lesser extent, the chemical nature of thesubstances utilized determines the consistency. Thus, the pressure ofstructural elements derived from carboxylic acids which are alkylated atthe unsaturated C-atom causes an increase in the hardness of the endproduct. The expert is thus enabled to adjust the consistency andelasticity of the end product by suitable composition of the amounts ofthe components (a) and (b).

The content of the components (a), (b) and (c) of the copolymers usedcan also be modified to achieve the desired water solubility of the filmformer. Thus, copolymers with increasing content of component (a)display increasing solubility in organic solvents and, decreasingsolubility in water and vice versa. The water solubility, however,depends primarily on the content of component (c) and only secondarilyon the content of the component (b). The ethanol solubility of thecopolymers depend primarily on the content of component (b). Copolymerswhich contain 40 to 90 percent by weight of vinyl esters, and 60 topercent by weight of monoesters of aliphatic, olefinically unsaturatedmonoand dicarboxylic acids with lower alkanediols and 0 to 10 percent byweight of a,fl-unsaturated carboxylic acids are generally used. Per 100parts by weight of the monomer mixture, there are generally used ascomponent (a) 90 to 40 parts by weight (preferably 80 to 60 parts byweight) of a vinyl ester or of a vinyl ester mixture whose compositionis determined by the desired elasticity and consistency of the endproduct, and as component (b) 10 to 60 parts by weight (preferably 20 to40 parts by weight) of an ester of an aliphatic mfl'unsaturateddicarboxylic acid with a lower aikanediol, or of a mixture of an esterof an aliphatic oz,fl-unsaturated monocarboxylic acid with a loweralkanediol and as component (c) 0 to 10 parts by weight of ancap-unsaturated carboxylic acid whose proportion is governed by theamount of neutralizable carboxyl groups in the end product necessary forthe achievement of the desired water solubility. This is determined bythe acid number of the polymer, i.e., the amount of liOl-l in mgnecessary to neutralize the free acids present in l g of the polymer.Generally polymers with an acid number of between 20 and 60 exhibitsuitable water solubility upon complete neutralization. Theneutralization of the carboxyl groups which is necessary for theachievement of the desired water solubility of the end products can beundertaken with a base, and effected either subsequent to thecopolymerization, particularly if the copolymerization is carried out ina water soluble solvent such as, a lower-molecular aliphatic alcohol,acetone or methyl ethyl ketone, or the neutralization can be effected ina solution prepared from the unneutralized acidic resin with a solventpreferably with a lower-molecular a1- cohol. The amount of the base tobe used is governed by the desired degree of neutralization. In general,however, as complete as possible a neutralization of the carboxyl groupspresent in the copolymer is striven for.

Furthermore, the molecular weight influences the properties of thecopolymers with a view to their technical usefulness. It has provedadvantageous to use copolymers with low molecular weight, the limitingviscosity number of which ranges between about 0.08 and 0.30 dl/gcopolymers of such kind can easily be prepared by using regulators suchas buturaldehyde 0r mercaptans in the preparation of the copolymer.

For the manufacture of the sprayable hair fixative preparations, thecopolymers generally in the form of powders, are conveniently dissolvedin 5 to 15 parts by weight of a water-soluble solvent advantageouslyethyl or isopropyl alcohol, with the addition of another organic solventsuch as methylene chloride, if required. The resulting clear solution isneutralized by the addition of a base, preferably a higher-boilingalkanolamine. Additives which are usual in cosmetics, e.g., softeners,perfume essences, dyes, brightening agents and other hair dressingagents are then incorporated into the solution. The solutionsconveniently contain not more than 9 to 12 percent of polymer,preferably about 10 percent. The polymer solution is filled into aerosolvessels and treated at room temperature under pressure with a suitableliquefied polyhalogenated hydrocarbon or mixtures thereof as apropellant. The solutions are used by spraying from these aerosolvessels by means of valves of known construction. The ratio between thepolymer solution and the propellant can vary within moderately widelimits. It depends on the desired content of solids in the finishedpreparation and on the propellant power of the polyhalogenatedhydrocarbons employed. Advantageously, the proportion by weight ofpolymer solution to propellant is between 1:1 and 1:4, preferably at1:2:3.

The commercially available polyhalogenated hydrocarbon propellants,e.g., trichlorofluoromethane, dichlorodifluoromethane and sym.tetrafluoroethane are suitable. However, other suitable propellants,e.g., propane, butane, carbonic acid, vinyl chloride and the like canalso be used. Mixtures of these propellants can be used to achievedesired propellant power.

In the following Examples, by parts are understood parts by weight andtemperatures are in degrees C.

EXAMPLE 1 A mixture of 87 parts of vinyl acetate, 10 partsof crotonicacid fl-hydroxyethyl ester, 3 parts of crotonic acid, 10 parts ofbutyraldehyde and 400 parts of water containing 1.4 parts of sodiumbicarbonate is heated to 67 in a stirring flask under nitrogen. Amixture of 1.3 parts of dibenzoyl peroxide and 1.8 parts of potassiumperoxydisulphate is then added and, during a time period of 4% hours,the bath temperature is increased to After brief introduction of steam,the resin is precipitated by addition of 5 parts 2-N hydrochloric acid,isolated, and dried in vacuum. The product obtained is a yellowishbrittle resin, whose limiting viscosity number in acetone, 25, is 0.1dl./g and its acid number is 21.5.

EXAMPLE 2 A mixture of 72 parts of vinyl acetate, 25 parts of crotonicacid fl-hydroxyethyl ester, parts of crotonic acid, parts ofbutyraldehyde and 400 parts of water containing 1.4 parts of sodiumbicarbonate is heated to 67 in a stirring flask under nitrogen. Amixture of 3.4 parts of potassium peroxydisulphate and 1.3 parts ofdibenzoyl peroxide is then added and, during a time period of 7 hours,the bath temperature is increased to 95. After brief introduction ofsteam, the resin is precipitated by addition of parts of 2-Nhydrochloric acid, isolated, and dried in vacuum. The end product is ayellowish, brittle resin whose limiting viscosity number in acetone, 25,is 0.08 dl./g and its acid number is 32.6.

EXAMPLE 3 A mixture of 65.5 parts of vinyl acetate, 29.5 parts ofcrotonic acid fl-hydroxyethyl ester, 5 parts of crotonic acid, 10 partsof butyraldehyde and 400 parts of water containing 2.4 parts of sodiumbicarbonate is heated to 67 in a stirring flask under nitrogen. Amixture of 3.9 parts of potassium peroxydisulphate and 1.5 parts ofdibenzoyl peroxide is then added and, within a time period of 7 hours,the bath temperature is increased to 95. After brief introduction ofcompressed air, the resin is precipitated in a separate flask byaddition of 15 parts of 2-N hydrochloric acid, isolated, and dried invacuum. The end product is a yellowish, brittle resin whose limitingviscosity number in acetone, 25 is 0.08 dl./g and its acid number is29.3.

EXAMPLE 4 A mixture of 72 parts of vinyl acetate, 5 parts of vinylpropionate, parts of crotonic acid B-hydroxyethel ester, 3 parts ofcrotonic acid, 10 parts of butyraldehyde and 400 parts of watercontaining 1.4 parts of sodium bicarbonate is heated to 67 in a stirringflask under nitrogen. A mixture of 2.9 parts of potassiumperoxydisulphate and 1.3 parts of dibenzoyl peroxide is then added and,within a time period of 6 hours, the bath temperature is increased to95. After brief introduction of steam, the resin is precipitated byaddition of 15 parts of 2-N hydrochloric acid, isolated, and dried invacuum. The end product is a yellowish, brittle resin whose limitingviscosity numberin acetone, is 0.09 dl./g and its acid number is 37.8.

EXAMPLES A mixture of 57 parts of vinyl acetate, 15 partsof vinylpropionate, 20 parts of crotonic acid fi-hydroxyethyl ester, 8 parts ofcrotonic acid and 400 parts of water containing 3.9 parts of sodiumbicarbonate is heated to 67 in a stirring flask under nitrogen. Amixture of 2.9 partsof potassium peroxydisulphate and 1.3 parts ofdibenzoyl peroxide is then added and, within a time period of 10 hours,the bath temperature is increased to 95. After brief introduction ofsteam, the resin is precipitated by addition of 15 parts of 2-Nhydrochloric acid, isolated, and dried in vacuum; the product obtainedis a colorless, viscous/hard resin whose limiting viscosity number inacetone, 25 is 0.28 dlJg and its acid number is 35.8.

EXAMPLE 6 I parts of sodium bicarbonate is heated to 68 in a stirringflask under nitrogen. A mixture of 3 parts of potassium peroxydisulphateand 1.2 parts of dibenzoylperoxide is then added and, within a timeperiod of 4.6 hours, the bath temperature is increased to 95. Afterbrief introduction of steam, the resin is isolated by addition of 1.5parts of 2-N hydrochloric acid and dried in vacuum. The product obtainedis a yellowish, viscous/hard resin whose limiting viscosity number inacetone, 25 is 0.09 dl./g and its acid number is 52.8.

EXAMPLE 7 A mixture of parts of vinyl acetate, 30 parts of acrylic acidB-hydroxyethyl ester, 670 parts of methyl ethyl ketone and 170 parts ofwater is heated at in a stirring flask under nitrogen in a heating bath,then a mixture of 1.8 parts of potassium peroxydisulphate is added andthe mixture is polymerized for 20 hours. The polymer is precipitatedfrom the resulting clear solution by addition of acetone, isolated, anddried in vacuum. The end product is a colorless, soft resin whoselimiting viscosity number in water, 25 is 0.1 dl./g.

EXAMPLE 8 A mixture of 87 parts of vinyl acetate, 13 parts of maleicacid mono-B-hydroxyethyl ester, 0.6 parts of dioctyl sodiumsulphosuccinate and 200 parts of water containing 3.2 parts of sodiumbicarbonate is heated to 68 in a stirring flask under nitrogen. Amixture of 1.3 parts of dibenzoyl peroxide and 1.4 parts of potassiumperoxydisulphate is added and, within 1.3 hours, the temperature israised to After brief introduction of steam, the resin is thenprecipitated by addition of 15 parts of 2-N hydrochloric acid, isolatedand dried in vacuum. The product obtained is a v colorless,viscous/hard, odorless resin whose limiting viscosity number in acetone,25? is 0.5 dl./g.

EXAMPLE 9 One Part of the product of Example 1 is dissolved in 9 partsof absolute ethanol and neutralized by addition of 0.04 parts ofdiethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfumeoil are thereupon added, and the mixture is filled into aerosol pressurevessels.

18 parts of fluorotrichloromethane and 12 parts of EXAMPLE 10 One partof the product of Example 2 is dissolved in 9 parts of absolute ethanoland neutralized by addition of 0.06 parts of diethanolamine. 0.01 partsof a silicone oil and 0.05 parts of perfume oil are then added, and

the mixture is filled into aerosol pressure vessels. 18 parts offluorotrichloromethane and 12 parts of difluorodichloromethane are thenadded under pressure. Hair treated with the preparation obtained isfixed well and is capable of being combed without trouble, practicallyno formation of scale on the comb and hair occurring. The good adhesivepower of the resin prevents the collapse of the hairdo. By simplerinsing of the hair with water, the resin is completely removabletherefrom. The film is not hygroscopic and its properties are unaffectedby atmospheric moisture.

EXAMPLE 11 One part of the product of example 3 is dissolved in 9 partsof absolute ethanol and neutralized by addition of 0.08 parts oftriethanolamine. After the addition of 0.01 parts of a silicone oil and0.05 parts of perfume, the mixture is filled into aerosol pressurevessels. 18 parts of fluoro-trichloromethane and 12 parts ofdichloromethane are then added under pressure.

A sprayable hair dressing agent is thus obtained which binds the hairwell and, because of its good adhesive power, permits no formation ofscale on the comb and hair on combing. The resin can be completelyremoved from the hair by simple shampooing.

EXAMPLE 12 One part of the product of Example 4 is dissolved in 9 partsof absolute ethanol and neutralized by addition of 0.04 parts ofdiethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfumeoil are thereupon added. The mixture is then tilled into aerosolpressure vessels to which 18 parts of fluorotrichloromethane and 12parts of difluorodichloromethane are then added under pressure. Asprayable hair fixative is thus obtained which binds the hair well andis capable of being combed without the formation of scale on comb andhair. The resin can be completely removed from the hair by simpleshampooing, and is resistant to moist atmospheres.

EXAMPLE 13 0.8 parts of the product of Example is dissolved in 9 partsof absolute ethanol and neutralized by addition of 0.1 1 parts ofdiethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfumeoil are thereupon added. The mixture is then filled into aerosolpressure vessels to which 18 parts of fluorotrichloromethane and 12parts of clifluorodiehloromethane are then added under pressure. l-lairsprayed with the hair fixative obtained is solidly bound, exhibits afine gloss and low susceptibility to electrostatic charge. It can berapidly and completely removed from the hair by a simple shampoo, and isresistant to moist atmospheres.

EXAMPLE 14 One part of the product of Example 6 is dissolved in 9 partsof absolute ethanol and neutralized by addition of 0.1 parts ofdiethanolamine. After the addition of about 0.05 to 0.06 parts ofcosmetic additives, the mixture is filled into aerosol pressure vessels.18 parts of fluorotrichloromethane and 12 parts ofdifluorodichloromethane are then added under pressure.

Hair treated with this hair dressing agent is well bound, displays finegloss and low susceptibility to electrostatic charge. The hair lacquermay be removed from the hair by normal shampooing and is resistant tomoist atmospheres.

EXAMPLE 15 One part of the product of Example 8 in 9 parts of absoluteethanol is neutralized by addition of 0.06 parts of diethanolamine,treated with 0.05 parts of cosmetic additives and diluted by addition of30 parts of water.

Hair, which can also be moist from preceding haircosmetic processes,which is treated with this aqueousalcoholic solution is, after dryingand combing, well and lastingly fixed and retains its naturalappearance. The hair dressing agent can be removed from the hair bysimple washing.

EXAMPLE 16 A mixture of 52 parts of vinyl acetate, 20 parts of vinylpropionate, 8 parts of crotonic acid, 20 parts of crotonic acidB-hydroxyethyl ester and 20-parts of methyl ethyl ketone is heated at 75in a stirring flask under pure nitrogen, then a mixture of 1 part ofdibenzoyl peroxide and 1.7 parts of dilauroyl peroxide is added and themixture is polymerized for 16-20 hours at 80-85. The clear solutionobtained is mixed with 95 parts of acetone and the polymer precipitatedin 350-420 parts of a petroleum ether diisopropyl ether mixture (123,3volumes), isolated and dried in vacuo. The end product is a colorlessand odorless brittle resin whose limiting viscosity number in acetone,25 is 0.1 dl/g and its acid number is 58.6.

EXAMPLE 17 One part of the resin obtained in Example 16 is dissolved in9 parts of absolute ethanol and neutralized by addition of 0.11 part ofdiethanolamine. 0.01 part of a silicone oiland 0.05 part of perfume oilare then added,

and the mixture is filled into aerosol pressure vessels. 18 parts offluorotrichloro-methane and 12 parts of difluorodichloro-methane arethen added under pressure. Hair treated with the preparation obtainedhas a high gloss and is capable of being combed without trouble,practically no formation of scale on the comb and hair occurring. Bysimple rinsing of the hair with water,

the resin is completely removable therefrom.

EXAMPLE 18 fitted with a stirrer, a thermometer, a gas inlet tube and areflux column, and heated to 7 5 under pure nitrogen. An initiatormixture of 9.2 parts of dibenzoyl peroxide and 15.8 parts of dilauroylperoxide is then added, and the polymerization is carried out for 16hours at The clear viscous solution thus obtained is dissolved in 630parts of acetone, and the polymer is precipitated therefrom in a mixtureof 1.45 parts diisopropyl ether and 2.6 parts of petroleum ether. Afterdrying in vacuo,

a colorless brittle resin is obtained, whose limiting viscosity numberin acetone, 25 is 0.1 dl/g and its acid number is 56.6.

EXAMPLE 19 A mixture of 57 parts of vinyl acetate, 15 parts of vinylisostearate, 8 parts of crotonic acid, 20 parts of crotonic acidB-hydroxyethyl ester and 25 parts of methyl ethyl ketone is heated at 75in a stirring flask under pure nitrogen, then a mixture of 1 part ofdibenzoyl peroxide and 1.7 parts of dilauroyl peroxide is added and themixture is polymerized for 17-20 hours at 80 -85. The clear solutionobtained is mixed with 95 parts of acetone and the polymer precipitatedin 350 parts of a petroleum ether diisopropyl ether EXAMPLE 20 One partof the resin obtained in Example 19 is dissolved in 9 parts of absoluteethanol and neutralized by addition of 0.11 part of diethanolamine. 0.01part of a silicone oil and 0.06 part of perfume oil are then added, andthe mixture is filled into aerosol pressure vessels. 18 parts offluorotrichloromethane and 12 parts of difluorodichloro-methane are thenadded under pressure. The hair dressing agent thus obtained binds thehair softly and imparts an agreable grasping to it. The resin can becompletely removedfrom the hair by simple washing.

1 claim:

1. A pressurized aerosol hair spray composition containing for each partby weight of a 9 to 12 percent ethanolic or isopropanolic solution of aneutral film forming copolymer having an acid number of about 20 toabout 60 prior to neutralization and having a limiting viscosity numberof from about 0.08 to 0.30 dl./g. comprising essentially a. from aboutto 40 percent by weight of a vinyl ester or mixtures thereof representedby the formula wherein R is selected'from the group consisting ofhydrogen and lower alkyl containing up to four carbon atoms,

b. from about 10 to 60 percent by weight of a monoester selected fromthe group consisting of. acrylic acid monoethyleneglycol ester,methacrylic acid monoethyleneglycol ester, crotonic acidmonoethyleneglycol ester, crotonic acid monopropyleneglycol ester,maleic acid monoethyleneglycol ester and a-chloroacrylic acidmonoethyleneglycol ester; and

. from 0 to about 10 percent by weight of an a,fi-unsaturated carboxylicacid represented by the formula wherein R is selected from the groupconsisting of hydrogen and carboxyl; R and R each are selected from thegroup consisting of hydrogen, halogen and lower alkyl containing up tofour carbon atoms; about 1 to about 4 parts by weight of a propellant.

